US20220393210A1 - Method of producing membrane-electrode assemblies and machine therefore - Google Patents
Method of producing membrane-electrode assemblies and machine therefore Download PDFInfo
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- US20220393210A1 US20220393210A1 US17/774,033 US202017774033A US2022393210A1 US 20220393210 A1 US20220393210 A1 US 20220393210A1 US 202017774033 A US202017774033 A US 202017774033A US 2022393210 A1 US2022393210 A1 US 2022393210A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/005—Producing membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/0046—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
- B32B37/0053—Constructional details of laminating machines comprising rollers; Constructional features of the rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
- B32B37/003—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid air inclusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
- B32B37/22—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of both discrete and continuous layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method and system for producing membrane-electrode assemblies.
- MEA membrane-electrode assembly
- PEM proton exchange membrane
- the electrode has three layers, namely, gas-diffusion, microporous and catalytic layers (GDL, MPL and CL, respectively).
- GDL, MPL and CL gas-diffusion, microporous and catalytic layers
- the polymer membrane typically Nafion
- Sheets of GDL with or without MPL are laminated onto the roll of the catalyst-coated membrane.
- the high-temperature PEM fuel cells use polymer membranes wetted with strong electrolytes, for example orthophosphoric acid-doped polybenzimidazole (H 3 PO 4 —PBI).
- H 3 PO 4 —PBI orthophosphoric acid-doped polybenzimidazole
- This acid-doped membrane provides high electrical conductivity at elevated temperatures, for example at 120-180° C., where the use of membranes based on NafionTM is impossible, see in this context also reference [2].
- Use of phosphoric acid as electrolyte liquid for doping of membranes is also disclosed in EP 1230705 B1 and US 2010/0279197 (ref [26]-[27])
- US 2007/0289707 A1 (ref [23]) describes a method for producing a membrane-electrode assembly comprising the steps of providing a continuous strip of an ionomer membrane, providing electrodes for assembly with the membrane strip and attaching the electrodes to the liquid-doped membrane strip, laminating the electrodes onto the strip in a calendering lamination station by guiding the strip in between two oppositely positioned lamination rollers, and compressing the electrodes and the strip for lamination by the two lamination rollers.
- the lamination rollers in US 2007/0289707 A1 has a continuous flushed surface which presses on the entire surface area of the electrodes and strip. Thus, surplus electrolyte is not removed from the edge regions of the strip during compressing.
- a method of producing a membrane-electrode assembly, MEA is described herein wherein a quasi-endless strip of a membrane material doped with a liquid electrolyte is provided, onto which electrodes are attached.
- the combination of a doped membrane strip and electrodes that are then laminated onto the strip in a calendering lamination station by guiding the strip in between two oppositely positioned lamination rollers and compressing the electrodes with the strip for lamination by the two lamination rollers.
- quadsi-endless is used herein for a long strip from a roll, which during the concrete process appears as not ending, although the roll eventually will be used up in the process.
- endless is sometimes used instead of “quasi-endless”.
- a machine for producing the membrane-electrode assembly, MEA.
- the machine comprises a membrane supply station with a first roller for supplying an endless strip of a membrane material doped with a liquid electrolyte.
- the electrode supply station comprises an electrode supply station with a pair of opposite electrode supply rollers, the supply rollers placing the electrodes onto one side, but typically both sides, of the membrane strip.
- the electrode supply station is configured for placing electrodes onto the membrane strip, typically one or two at a time, with a predetermined longitudinal spacing between consecutive electrodes on the strip.
- a first conveyor For conveying the strip from the membrane supply station through the electrode supply station between electrode supply rollers, a first conveyor is used.
- the electrode supply rollers of the electrode supply station are vacuum rollers for fixing the electrodes against the electrode supply rollers by suction, until the electrodes are deposited onto the membrane strip.
- Such rollers are useful in case that the electrodes are not provided as an endless strip but provided as sheets, for example after cutting them from an endless strip into pieces that match the final size of the MEA in the fuel cell.
- the strip with the membrane and electrodes is conveyed on a conveyor to a lamination station, which comprises lamination rollers for pressing the electrodes onto the strip in a lamination process, optionally at temperatures elevated above room temperature, for example above 100° C.
- a binder is used for binding the electrodes onto the membrane strip in the lamination process.
- the binder is a polymer and has a glass transition temperature, and the temperature for the lamination process is adjusted to a temperature above the glass transition temperature.
- the temperature should be above 110° C. in the lamination process.
- the temperature for the production should not exceed a temperature detrimental to the dopant.
- the dopant is H 3 PO 4
- the temperature should be below 150° C. in order to avoid bubbles in the electrolyte.
- Such dopant is used for polybenzimidazole, PBI, membranes, optionally for use in high-temperature PEM fuel cells.
- the strip has a first width and the electrodes have a second width that is less than the first width.
- the electrodes are combined with and attached to the liquid-doped membrane strip, the electrodes are positioned between the two opposite side-edge regions of the strip. These edged regions are not being covered by the electrodes.
- such membrane strip with the electrodes remote from the edges of the strip is conveyed through a further calendering station, wherein oppositely placed calendering rollers press on the edge regions of the strip but not on the electrodes, or at least press less on the electrodes than on the edge regions.
- the doping liquid is pressed out of the edge regions but not out of the area under the electrodes. This is important in that it provides a correct doping of electrolyte under the electrodes but prevents presence of electrolyte at locations where it is not needed, namely at the edge region of the strip. This has the advantage that the electrolyte is only provided where it is needed and does not lead to early malfunctioning of the fuel cell.
- the further calendering station is provided with at two calendering rollers located opposite to each other and facing each other with parallel rotation axes, wherein the calendering rollers have a central region matching the location of the electrodes when attached to the strip and a side region matching the side edge region of the strip when the strip with the electrodes is guided through the calendering region.
- the central region of at least one of the calendering rollers is provided as a cavity, optionally having a depth of at least half of a thickness of the strip with the electrodes, in order for the calendering roller to press along the side edge regions of the strip but not onto the electrodes or at least much less onto the electrodes than onto the side regions.
- both calendering rollers with one roller on either side of the strip are provided with such cavity.
- the at least one of the calendering rollers comprises, in addition to the side region and the cavity, a cross bar extending from one side region to the opposite site region.
- the cross bar presses onto the strip at the locations of the spaces between the electrodes during the transport of the strip through the calendering station. It is understood that the motion of the strip through the calendering station and the dimensioning and speed of the calendering rollers are dimensioned to be synchronized with the strip movement so that the rotation of the rollers leads to the bar actually pressing in between the electrodes.
- the assembly of a fuel cell stack is automatic.
- the MEA strip is conveyed to a cutting station for cutting the strip into separate MEAs.
- the machine further comprises a bipolar plate supply station for automatically supplying bipolar plates, BPP.
- the machine is then further configured for automatically assembling a fuel cell stack by providing end plates for the fuel cell stack and for inserting the separate MEAs automatically in between multiple subsequently stacked bipolar plates.
- the invention provides a method of producing a membrane-electrode assembly, MEA, where a quasi-endless strip of a membrane material doped with a liquid electrolyte is laminated with electrodes, and wherein edge regions of the strip as well as spaces between the electrodes are pressed free from surplus electrolyte.
- this production technique can also be applied for membrane components in other devices for power production or energy storage, as well as for conversion devices having bipolar design, for example batteries, electrical double-layer capacitors, electrolyzers, and generally in fuel cells.
- conversion devices having bipolar design for example batteries, electrical double-layer capacitors, electrolyzers, and generally in fuel cells.
- it has particular interest and advantages when used for MEAs in high-temperature PEM fuel cells.
- FIG. 1 is a scheme of a fuel cell stack assembling process with roll-to-roll MEA fabrication
- FIG. 2 are diagrams illustrating curves for (a) polarization and (b) power for MEAs produced via calendering at different temperatures;
- FIG. 3 are diagrams for adsorption isotherms for a H 3 PO 4 —PBI system describing (a) slow and (b) fast processes for acid doping of membranes;
- FIG. 4 is a drawing showing measurements for re-distribution of orthophosphoric acid in MEAs after their calendering through a calendering lamination station at different temperature and speed;
- FIG. 5 is a drawing illustrating (a) a design of rollers in a second calendering station for compressing regions where there are membranes only but not electrodes and (b) an illustration of part of the MEA roll after the lamination station;
- FIG. 6 is a drawing showing measurements of re-distribution of orthophosphoric acid in a MEA after its calendering through the lamination station and through the second calendering station;
- FIG. 7 is a drawing illustrating differences in the visible electrode area and the active area for MEAs (a) without and (b) with PI gaskets;
- FIG. 8 shows polarization curves for MEAs with and without PI gaskets where the current is normalized (a) by the visible electrode area and (b) by the active area.
- FIG. 1 illustrates a scheme of a fuel cell stack assembling process including roll-to-roll MEA fabrication.
- An orthophosphoric acid-doped polybenzimidazole (H 3 PO 4 —PBI) quasi-endless membrane film strip is provided on a membrane film roll 1 and unwound from its support film, which, in turn, is rolled onto support film roller 3 .
- the support film is potentially a polyester film, for example polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- electrodes are unwound from electrode rolls 4 , while possible protective films, for example cellulose films, are removed onto roller 5 .
- the unwound electrodes are cut into the correct size by knives 7 and held by vacuum in correct position on the vacuum rollers 6 . Due to the PBI film being moved in between the vacuum rollers 6 , the cut electrodes, which are held and transported by the vacuum rollers 6 to the membrane strip, are placed at predetermined positions onto opposite sides of the PBI membrane strip surfaces.
- the strip comprises consecutive sheets of electrodes on opposite sides of the strip, and the electrode-loaded strip is further guided by guiding rollers 8 until it passes through lamination rollers 9 of a first calendering station, which is a lamination station, where electrodes are laminated under pressure onto the surface of the membrane film strip.
- Cleaning rollers 11 are used to clean the lamination rollers 9 from orthophosphoric acid.
- Lamination rollers 9 can be kept at room temperature or optionally heated to elevated temperatures, for example to above 100° C., in order to enhance adhesion between the CL and the PEM.
- PTFE is used as an electrode binding agent
- temperatures higher than 150° C. are undesirable due to the increased risk of evaporation of the orthophosphoric acid as well as water bubble formation therein, see reference [17].
- the temperature ranges as per Table 1 are especially useful for the MEA fabrication process.
- the temperatures in Table 1 are based on data given above as well as data of upper glass transition temperatures for other commonly used polymer binders, see references [18, 19].
- the temperature range of 125 ⁇ 5° C. yields better electrochemical performance than a MEA produced at room temperature, i.e. at 25 ⁇ 5° C.
- FIG. 2 diagrams are illustrating curves for (a) polarization and (b) power for MEAs produced via lamination calendering at different temperatures. It is clearly observed that the higher temperature results in better performance.
- Another important parameter of the MEA's fabrication besides temperature during lamination is the speed of the rotation of the calendering machine, because the speed defines how long a MEA will be under pressure.
- the time of pressure onto the MEA affects the re-distribution of orthophosphoric acid within the MEA. Such redistribution is not desired if it leads to an inhomogeneous distribution of the acid. This effect sets a lower limit for the speed, as the speed should not be so slow that substantial redistribution takes place.
- FIG. 3 are diagrams for adsorption isotherms for a H 3 PO 4 —PBI system describing (a) slow and (b) fast acid doping processes of membranes. If the doping process is slow at relatively low temperature, the resulting effect is largely a monomolecular adsorption mechanism, while a fast doping process at elevated temperature is characterized by a change from monomolecular to a polymolecular adsorption, which leads to acid over-doping of the PBI membrane, where distances between polymer chains become longer. This, in turn, implies that the membrane structure is changed from film-like to gel-like with partially dissolution of PBI in H 3 PO 4 . Gelatinization is highly undesirable because the membrane is losing its strength and elasticity, which may have negative effects on the lifetime of the entire fuel cell stack. Accordingly, this effect sets an upper limit for the speed at which the process can be performed.
- the speed and temperature should not be too high, as this leads to gel formation, and the speed and temperature should not be too low, as this leads to re-distribution and inhomogeneity. Therefore, a proper regime of speed has to be found experimentally for the process. However, not only the speed has to be adjusted correctly, also the related temperature for the lamination process must be selected correctly. This is a complex task.
- FIG. 4 illustrates measurements of content of orthophosphoric acid in terms of mg/cm 2 on an 80 ⁇ m thick PBI membrane film.
- Four pieces of PBI film are shown, each having a grey central area that illustrates the electrodes on the PBI film membrane, which is outlined with white edge regions. Measurements were made on different locations on the shown pieces of PBI membrane, including at the corners, midway between the corners, and at three locations on the electrode, namely at the opposite ends of the electrode and midway therein between.
- the upper of the four pieces of membranes was laminated at a temperature of 25° C. and a relative speed of 20 rpm of the calendering roller. It is seen that the corners of the piece have acid content ranging from 9.7 in the lower edge region to 17.5 in the lower left corner and 16.3 in the right edge. This is an undesired variation of almost a factor of 2 due to heavy re-distribution of the acid because of low temperature despite high speed.
- an example of a useful maximum level of orthophosphoric acid in the PBI membrane is 14.5 mg/cm 2 per 80 ⁇ m thickness.
- this level is strongly depended on the PBI-type that is used in the membrane, e.g. poly[2,5-benzimidazole] (ABPBI), poly[2,2′-m-(phenylene)-5,5′-bibenzimidazole] (m-PBI) or poly[2,2′-p-(phenylene)-5,5′-bibenzimidazole (p-PBI), on molar mass of the polymer, and on the presence of additives therein, as well as other factors, due to different adsorption capacity of the membranes, see also references [20-22].
- FIG. 5 a is illustrating a design of a roller 10 in such a second calendering station for compressing an area at the edge regions where only membrane is present but no electrodes.
- FIG. 5 b illustrates the corresponding PBI film with the electrodes, which are shown as grey areas on top and bottom.
- the roller 10 in FIG. 5 a has a cavity/niche 26 which accommodates the electrodes during the calendering process, while edge regions 25 of the roller 10 are elevated relatively to the cavity 26 in order to press onto the corresponding edge regions of the PBI film.
- the roller 10 has a transverse bar 24 that presses the membrane film only between the electrode areas but does not press onto the electrode areas.
- the most important element in that design is the cavity/niche for the electrodes that have already been laminated onto the membrane. Such cavity/niche protects the electrode from over-compression.
- its depth 23 T is no less than half of the total thickness of the MEA after the MEA has passed the lamination station 9 .
- cleaning rollers 12 in FIG. 1 are used to clean the surface of the calendering rollers 10 .
- FIG. 6 shows measurements of re-distribution of orthophosphoric acid in MEA after its calendering through both the lamination station with lamination rollers 9 and the second calendering station with the calendering rollers 10 .
- orthophosphoric acid is distributed uniformly in the active area of the MEA—its average content is 9.3 mg/cm 2 with deviations of no more than 0.1 mg/cm 2 .
- the roll of MEAs is cut by a knife 13 to form sheets with single MEAs 14 , which are moved on the conveyor belt 15 to the assembly table 16 .
- the assembly table 16 has an adjustable height. Endplates for fuel cell stack are provided from magazine 17 and bipolar plate with gaskets from magazine 18 . Further, bolts 19 are delivered by means of corresponding conveyors.
- the build-up of the fuel cell stack occurs according to following step-by-step procedure with MEAs sandwiched between bipolar plates (BPP): For example, according to the following sequence:
- Plate 20 creates correct compression to the stack, when the bolts and nuts are tightened. Assembled in such way, the fuel cell stack 21 is transported by further conveyor belt 15 to the carrier located on a cargo robot 22 for its further storage.
- the proposed automated process of making MEAs and fuel cell stacks based on the MEAs has multiple advantages, such as continuity and fast speed by which high productivity and low costs are achieved.
- Uniform distribution of orthophosphoric acid in MEAs is properly controllable for avoiding critical levels.
- Two calendering stations are used, one for lamination and one for controlling acid levels at the edges and between the electrodes by local compression of predetermined parts of a MEA. This keeps the PBI membrane in a condition that is safe from dissolution by hot concentrated H 3 PO 4 even without using protective gaskets on the perimeter of a MEA.
- the illustrated MEA is a 3-layer sandwich construction of a membrane between two electrodes, which is advantageous in comparison with the prior art 5-layer structure as described in reference [14].
- the actual electrode area is the same for both MEAs in FIG. 7 , namely A ⁇ B cm 2 .
- the 3-layer MEA without PI gaskets has a visible electrode area which is equal to the active area, namely A ⁇ B
- this is not so for the 5-layer MEA with PI gaskets.
- the 5-layer MEA with PI gaskets has a smaller visible electrode area, because 2 mm of the electrode on the perimeter is covered by a PI gasket.
- about 1 mm of the electrode on each side under the PI gasket is not inert, it still results in an active area for the 5-layer MEA of (A ⁇ 0.2) ⁇ (B ⁇ 0.2) cm 2 . This implies that the prior art 5-layer MEA with the gaskets have a smaller active area if the overall dimensions of membrane and electrode otherwise are the same.
- FIG. 8 a shows polarization curves for MEAs with and without PI gaskets where the measured current is normalized to the visible electrode area (a). It is observed that the MEA with PI gasket has a slightly higher performance experimentally. However, when the results are normalized to the actual active area, as explained in relation to FIG. 7 , no difference was found, as already mentioned above. Accordingly, the method of the invention is proven to provide equally good results as the prior art but with a much simpler procedure where gaskets are avoided.
- the invention provides a continuous roll-to-roll process of MEA fabrication with already-doped membrane, in particular for high-temperature PEM fuel cells.
- the specific double calendering of the 3-layer MEA roll with only local compression along edge regions and between the electrodes protects the electrodes from disadvantageous pressure and avoids unwanted redistribution and overshooting of acid content. All in all, it leads to improved control of the dopant content and its distribution in the MEA.
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Abstract
Description
- The present invention relates to a method and system for producing membrane-electrode assemblies.
- A key part of a fuel cell is the membrane-electrode assembly (MEA) that contains two electrodes and a proton exchange membrane (PEM) between them. In general, the electrode has three layers, namely, gas-diffusion, microporous and catalytic layers (GDL, MPL and CL, respectively). In low-temperature PEM fuel cells, the polymer membrane, typically Nafion, is saturated with water. Generally, this does not pose a problem when coating the catalytic layers of the electrodes directly onto the surface of the membrane. Sheets of GDL with or without MPL are laminated onto the roll of the catalyst-coated membrane. A prior art process for producing MEAs is disclosed in U.S. Pat. No. 6,074,692, (ref [1]), which also discusses other prior art.
- Unlike low-temperature PEM fuel cells, the high-temperature PEM fuel cells use polymer membranes wetted with strong electrolytes, for example orthophosphoric acid-doped polybenzimidazole (H3PO4—PBI). This acid-doped membrane provides high electrical conductivity at elevated temperatures, for example at 120-180° C., where the use of membranes based on Nafion™ is impossible, see in this context also reference [2]. Use of phosphoric acid as electrolyte liquid for doping of membranes is also disclosed in EP 1230705 B1 and US 2010/0279197 (ref [26]-[27])
- Unlike water-saturated Nafion membranes, the presence of the orthophosphoric acid inside the membrane makes it difficult to coat a catalyst on the surface of the PBI membrane, and a coated CL requires rigorous drying to remove the solvents, for example iso-propanol and N-methyl-2-pyrrolidone, see also reference [3]. On the other hand, coating the CL onto the dry, undoped PBI membrane creates other difficulties due to the necessity of impregnation with acid, see reference [4]. Several research groups apply decal methods that allow transfer of dried CL onto the already doped membrane, after which the membrane is peeled off the substrate, leaving a CL-covered membrane only, see references [5-10]. However, such methods are not useful for fast, large-scale production.
- Although, the methods in the prior art provide various improvements, there is a need for methods and systems for large scale production. It should be mentioned that there have been attempts of implementing separated roll-to-roll production of electrodes and H3PO4—PBI membranes, see references [11, 12]. However, as discussed in these references, the methods still need refinements in order to overcome shortcomings, such as inhomogeneities.
- Other attempts are disclosed in U.S. Pat. No. 8,399,145, US2006/0014065, and U.S. Pat. No. 6,998,149 (references [13-15]) where protective tightening and gaskets are used at the side edges. Continuous lamination processes for polymer electrolyte membranes are also disclosed in US 2018/0290441 and US 2007/0116999 (ref [24]-[25]). However, also such approaches have shortcomings due to the methods becoming relatively complex in a roll-to-roll production process.
- US 2007/0289707 A1, (ref [23]) describes a method for producing a membrane-electrode assembly comprising the steps of providing a continuous strip of an ionomer membrane, providing electrodes for assembly with the membrane strip and attaching the electrodes to the liquid-doped membrane strip, laminating the electrodes onto the strip in a calendering lamination station by guiding the strip in between two oppositely positioned lamination rollers, and compressing the electrodes and the strip for lamination by the two lamination rollers. The lamination rollers in US 2007/0289707 A1 has a continuous flushed surface which presses on the entire surface area of the electrodes and strip. Thus, surplus electrolyte is not removed from the edge regions of the strip during compressing.
- Accordingly, there is still a need for further improvements.
- It is therefore the objective of the invention to provide an improvement in the art. Especially, it is an objective to provide an improved method and system for production of MEAs. In particular, it is an objective to provide methods and systems for large-scale production of MEAs, where the production is simple, easily automated, and a fast, continuous process.
- A method of producing a membrane-electrode assembly, MEA, is described herein wherein a quasi-endless strip of a membrane material doped with a liquid electrolyte is provided, onto which electrodes are attached. The combination of a doped membrane strip and electrodes that are then laminated onto the strip in a calendering lamination station by guiding the strip in between two oppositely positioned lamination rollers and compressing the electrodes with the strip for lamination by the two lamination rollers.
- The term “quasi-endless” is used herein for a long strip from a roll, which during the concrete process appears as not ending, although the roll eventually will be used up in the process. In the technical field, the term “endless” is sometimes used instead of “quasi-endless”.
- For performing the production, a machine is provided for producing the membrane-electrode assembly, MEA. In a concrete embodiment, the machine comprises a membrane supply station with a first roller for supplying an endless strip of a membrane material doped with a liquid electrolyte.
- Further, it comprises an electrode supply station with a pair of opposite electrode supply rollers, the supply rollers placing the electrodes onto one side, but typically both sides, of the membrane strip. For example, the electrode supply station is configured for placing electrodes onto the membrane strip, typically one or two at a time, with a predetermined longitudinal spacing between consecutive electrodes on the strip.
- For conveying the strip from the membrane supply station through the electrode supply station between electrode supply rollers, a first conveyor is used.
- In some concrete embodiments, the electrode supply rollers of the electrode supply station are vacuum rollers for fixing the electrodes against the electrode supply rollers by suction, until the electrodes are deposited onto the membrane strip. Such rollers are useful in case that the electrodes are not provided as an endless strip but provided as sheets, for example after cutting them from an endless strip into pieces that match the final size of the MEA in the fuel cell.
- After placement of the electrodes onto the membrane strip, the strip with the membrane and electrodes is conveyed on a conveyor to a lamination station, which comprises lamination rollers for pressing the electrodes onto the strip in a lamination process, optionally at temperatures elevated above room temperature, for example above 100° C.
- Optionally, a binder is used for binding the electrodes onto the membrane strip in the lamination process. In practical embodiments, the binder is a polymer and has a glass transition temperature, and the temperature for the lamination process is adjusted to a temperature above the glass transition temperature. For example, for polytetrafluoroethylene (PTFE), the temperature should be above 110° C. in the lamination process.
- However, the temperature for the production should not exceed a temperature detrimental to the dopant. For example, if the dopant is H3PO4, the temperature should be below 150° C. in order to avoid bubbles in the electrolyte. Such dopant is used for polybenzimidazole, PBI, membranes, optionally for use in high-temperature PEM fuel cells.
- In some concrete embodiments for the production method, the strip has a first width and the electrodes have a second width that is less than the first width. When the electrodes are combined with and attached to the liquid-doped membrane strip, the electrodes are positioned between the two opposite side-edge regions of the strip. These edged regions are not being covered by the electrodes.
- After the lamination station, such membrane strip with the electrodes remote from the edges of the strip is conveyed through a further calendering station, wherein oppositely placed calendering rollers press on the edge regions of the strip but not on the electrodes, or at least press less on the electrodes than on the edge regions. By doing so, the doping liquid is pressed out of the edge regions but not out of the area under the electrodes. This is important in that it provides a correct doping of electrolyte under the electrodes but prevents presence of electrolyte at locations where it is not needed, namely at the edge region of the strip. This has the advantage that the electrolyte is only provided where it is needed and does not lead to early malfunctioning of the fuel cell.
- In concrete embodiment, the further calendering station is provided with at two calendering rollers located opposite to each other and facing each other with parallel rotation axes, wherein the calendering rollers have a central region matching the location of the electrodes when attached to the strip and a side region matching the side edge region of the strip when the strip with the electrodes is guided through the calendering region. The central region of at least one of the calendering rollers is provided as a cavity, optionally having a depth of at least half of a thickness of the strip with the electrodes, in order for the calendering roller to press along the side edge regions of the strip but not onto the electrodes or at least much less onto the electrodes than onto the side regions. Typically both calendering rollers with one roller on either side of the strip are provided with such cavity.
- In those cases where the electrodes are provided as sheets, the positioning of the electrodes as pieces onto the strip implies the provision of spaces between the electrodes in a longitudinal direction of the strip, the following embodiment is useful. For example, the at least one of the calendering rollers comprises, in addition to the side region and the cavity, a cross bar extending from one side region to the opposite site region. When the circumference of the at least one calendering roller with the cavity is equal to the periodic length from one electrode to the next, the cross bar presses onto the strip at the locations of the spaces between the electrodes during the transport of the strip through the calendering station. It is understood that the motion of the strip through the calendering station and the dimensioning and speed of the calendering rollers are dimensioned to be synchronized with the strip movement so that the rotation of the rollers leads to the bar actually pressing in between the electrodes.
- In some aspects of the invention, also the assembly of a fuel cell stack is automatic. For example, after the lamination station and the further calendering station, the MEA strip is conveyed to a cutting station for cutting the strip into separate MEAs. Optionally, the machine further comprises a bipolar plate supply station for automatically supplying bipolar plates, BPP. The machine is then further configured for automatically assembling a fuel cell stack by providing end plates for the fuel cell stack and for inserting the separate MEAs automatically in between multiple subsequently stacked bipolar plates.
- As described above, the invention provides a method of producing a membrane-electrode assembly, MEA, where a quasi-endless strip of a membrane material doped with a liquid electrolyte is laminated with electrodes, and wherein edge regions of the strip as well as spaces between the electrodes are pressed free from surplus electrolyte.
- It should be noted here that this production technique can also be applied for membrane components in other devices for power production or energy storage, as well as for conversion devices having bipolar design, for example batteries, electrical double-layer capacitors, electrolyzers, and generally in fuel cells. However, it has particular interest and advantages when used for MEAs in high-temperature PEM fuel cells.
- The invention will be explained in more detail with reference to the drawings, wherein
-
FIG. 1 is a scheme of a fuel cell stack assembling process with roll-to-roll MEA fabrication; -
FIG. 2 are diagrams illustrating curves for (a) polarization and (b) power for MEAs produced via calendering at different temperatures; -
FIG. 3 are diagrams for adsorption isotherms for a H3PO4—PBI system describing (a) slow and (b) fast processes for acid doping of membranes; -
FIG. 4 is a drawing showing measurements for re-distribution of orthophosphoric acid in MEAs after their calendering through a calendering lamination station at different temperature and speed; -
FIG. 5 is a drawing illustrating (a) a design of rollers in a second calendering station for compressing regions where there are membranes only but not electrodes and (b) an illustration of part of the MEA roll after the lamination station; -
FIG. 6 is a drawing showing measurements of re-distribution of orthophosphoric acid in a MEA after its calendering through the lamination station and through the second calendering station; -
FIG. 7 is a drawing illustrating differences in the visible electrode area and the active area for MEAs (a) without and (b) with PI gaskets; -
FIG. 8 shows polarization curves for MEAs with and without PI gaskets where the current is normalized (a) by the visible electrode area and (b) by the active area. - In the following, examples are given for how to realize high-speed roll-to-roll fabrication of 3-layer MEAs that do not have protective gaskets along their edge regions. This is different from the procedures as disclosed in references [13-15]. Described are also potential fuel cells and fuel cell stacks based on the MEAs.
-
FIG. 1 illustrates a scheme of a fuel cell stack assembling process including roll-to-roll MEA fabrication. An orthophosphoric acid-doped polybenzimidazole (H3PO4—PBI) quasi-endless membrane film strip is provided on amembrane film roll 1 and unwound from its support film, which, in turn, is rolled onto support film roller 3. The support film is potentially a polyester film, for example polyethylene terephthalate (PET). The remaining doped PBI membrane film strip is guided over guider roller 2 and moved in between twovacuum rollers 6. - As part of the continuous process, electrodes are unwound from electrode rolls 4, while possible protective films, for example cellulose films, are removed onto
roller 5. The unwound electrodes are cut into the correct size byknives 7 and held by vacuum in correct position on thevacuum rollers 6. Due to the PBI film being moved in between thevacuum rollers 6, the cut electrodes, which are held and transported by thevacuum rollers 6 to the membrane strip, are placed at predetermined positions onto opposite sides of the PBI membrane strip surfaces. - After these steps, the strip comprises consecutive sheets of electrodes on opposite sides of the strip, and the electrode-loaded strip is further guided by guiding
rollers 8 until it passes throughlamination rollers 9 of a first calendering station, which is a lamination station, where electrodes are laminated under pressure onto the surface of the membrane film strip.Cleaning rollers 11 are used to clean thelamination rollers 9 from orthophosphoric acid.Lamination rollers 9 can be kept at room temperature or optionally heated to elevated temperatures, for example to above 100° C., in order to enhance adhesion between the CL and the PEM. - For example, if PTFE is used as an electrode binding agent, it is advantageous to carry out the calendering lamination process at 110-130° C., because PTFE transforms from crystalline form to a rigid amorphous state at these temperatures, see reference [16]. On the other hand, temperatures higher than 150° C. are undesirable due to the increased risk of evaporation of the orthophosphoric acid as well as water bubble formation therein, see reference [17]. Thus, the temperature ranges as per Table 1 are especially useful for the MEA fabrication process. The temperatures in Table 1 are based on data given above as well as data of upper glass transition temperatures for other commonly used polymer binders, see references [18, 19].
-
TABLE 1 Desirable temperature ranges for assembling membrane and electrodes by to-roll-roll process Polymer binder Temperature range (° C.) Fluorinated ethylene (FEP) 54-150 Polytetrafluoroethylene (PTFE) 110-150 Polyvinylidene fluoride (PVDF) 30-150 - For example, for a MEA made of a H3PO4—PBI membrane and electrodes with a PTFE binding agent, the temperature range of 125±5° C. yields better electrochemical performance than a MEA produced at room temperature, i.e. at 25±5° C.
- In particular, use of elevated temperatures in the MEA's lamination process yields up to 25% increased power density. This is illustrated in
FIG. 2 , where diagrams are illustrating curves for (a) polarization and (b) power for MEAs produced via lamination calendering at different temperatures. It is clearly observed that the higher temperature results in better performance. - Another important parameter of the MEA's fabrication besides temperature during lamination is the speed of the rotation of the calendering machine, because the speed defines how long a MEA will be under pressure. The time of pressure onto the MEA affects the re-distribution of orthophosphoric acid within the MEA. Such redistribution is not desired if it leads to an inhomogeneous distribution of the acid. This effect sets a lower limit for the speed, as the speed should not be so slow that substantial redistribution takes place.
- On the other hand, the speed should also not be too high due to the following effect.
FIG. 3 are diagrams for adsorption isotherms for a H3PO4—PBI system describing (a) slow and (b) fast acid doping processes of membranes. If the doping process is slow at relatively low temperature, the resulting effect is largely a monomolecular adsorption mechanism, while a fast doping process at elevated temperature is characterized by a change from monomolecular to a polymolecular adsorption, which leads to acid over-doping of the PBI membrane, where distances between polymer chains become longer. This, in turn, implies that the membrane structure is changed from film-like to gel-like with partially dissolution of PBI in H3PO4. Gelatinization is highly undesirable because the membrane is losing its strength and elasticity, which may have negative effects on the lifetime of the entire fuel cell stack. Accordingly, this effect sets an upper limit for the speed at which the process can be performed. - The speed and temperature should not be too high, as this leads to gel formation, and the speed and temperature should not be too low, as this leads to re-distribution and inhomogeneity. Therefore, a proper regime of speed has to be found experimentally for the process. However, not only the speed has to be adjusted correctly, also the related temperature for the lamination process must be selected correctly. This is a complex task.
- In order to illustrate the dependency of the speed on re-distribution, reference is made to
FIG. 4 , which illustrates measurements of content of orthophosphoric acid in terms of mg/cm2 on an 80 μm thick PBI membrane film. Four pieces of PBI film are shown, each having a grey central area that illustrates the electrodes on the PBI film membrane, which is outlined with white edge regions. Measurements were made on different locations on the shown pieces of PBI membrane, including at the corners, midway between the corners, and at three locations on the electrode, namely at the opposite ends of the electrode and midway therein between. - The data presented in
FIG. 4 for the four pieces of membranes with electrodes relate to four different production methods, namely: - 25° C. at 20 rpm,
- 125° C. at 20 rpm,
- 25° C. at 2 rpm, and
- 125° C. at 2 rpm.
- As illustrated, the upper of the four pieces of membranes was laminated at a temperature of 25° C. and a relative speed of 20 rpm of the calendering roller. It is seen that the corners of the piece have acid content ranging from 9.7 in the lower edge region to 17.5 in the lower left corner and 16.3 in the right edge. This is an undesired variation of almost a factor of 2 due to heavy re-distribution of the acid because of low temperature despite high speed.
- It should be noted here that an example of a useful maximum level of orthophosphoric acid in the PBI membrane is 14.5 mg/cm2 per 80 μm thickness. However, this level is strongly depended on the PBI-type that is used in the membrane, e.g. poly[2,5-benzimidazole] (ABPBI), poly[2,2′-m-(phenylene)-5,5′-bibenzimidazole] (m-PBI) or poly[2,2′-p-(phenylene)-5,5′-bibenzimidazole (p-PBI), on molar mass of the polymer, and on the presence of additives therein, as well as other factors, due to different adsorption capacity of the membranes, see also references [20-22].
- When comparing pieces fabricated at low temperature with pieces fabricated at high temperature, it is observed from
FIG. 4 that the pieces fabricated at low temperature each have two locations that relate to yield acid levels higher than the maximum target value of 14.5, whereas the pieces fabricated at high temperature have only one of such locations exceeding the maximum set level. Accordingly, from the data inFIG. 4 , it can be concluded that higher temperatures are preferable for lamination of MEAs because fewer critical points are observed on the edge regions. In particular, there are 2 critical points at 25° C. and there is only 1 critical point at 125° C. for both speeds of 2 rpm and 20 rpm. - It was expected that reduction of the speed of the calendering machine would lead to acid re-distribution. This was also observed at 25° C. However, it was surprising that re-distribution was observed to a substantially lesser degree when the process is carried out at 125° C. However, such behavior can be explained by means of adsorption isotherm, see
FIG. 3 . It can be concluded that the doping process takes place rapidly at 125° C., i.e. acid has enough time to be distributed inside PBI membrane, and it is more uniformly re-doping the membrane, whereas at room temperature the acid mainly fills defected locations, e.g. cracks or pores. Although, increased time under compression allows to start a re-doping process at 25° C., the higher temperature lamination is preferable. - From these experiments, it could be concluded that a process at 125° C. is more robust than at room temperature.
- It should be noted that the acid content in MEAs within the active area is relatively stable regardless of the different calendering parameters, namely 10-11 mg/cm2. However, large variations are seen at the edge regions, which required further improvements.
- Especially, elimination of critically high acid content at the edge regions of the membrane strip is an important task in the fabrication of inner gasket-free MEAs, if these should have a long lifetime. This problem was solved by a second calendering station with calendering
rollers 10, seeFIG. 1 . These calenderingrollers 10 are special in that they only compress the edge area of the MEAs and squeeze the extra orthophosphoric acid out of the membrane. For optimum results, calendering rolls, as shown inFIG. 5 , were designed specifically for this purpose. -
FIG. 5 a is illustrating a design of aroller 10 in such a second calendering station for compressing an area at the edge regions where only membrane is present but no electrodes.FIG. 5 b illustrates the corresponding PBI film with the electrodes, which are shown as grey areas on top and bottom. Theroller 10 inFIG. 5 a has a cavity/niche 26 which accommodates the electrodes during the calendering process, whileedge regions 25 of theroller 10 are elevated relatively to thecavity 26 in order to press onto the corresponding edge regions of the PBI film. In addition, theroller 10 has atransverse bar 24 that presses the membrane film only between the electrode areas but does not press onto the electrode areas. - The most important element in that design is the cavity/niche for the electrodes that have already been laminated onto the membrane. Such cavity/niche protects the electrode from over-compression. Advantageously, its depth 23 T is no less than half of the total thickness of the MEA after the MEA has passed the
lamination station 9. - Notice that
cleaning rollers 12 inFIG. 1 are used to clean the surface of thecalendering rollers 10. - The final acid distribution after passing these two calendering stations with
respective rollers FIG. 6 similar to the measurement points inFIG. 4 .FIG. 6 shows measurements of re-distribution of orthophosphoric acid in MEA after its calendering through both the lamination station withlamination rollers 9 and the second calendering station with thecalendering rollers 10. As seen fromFIG. 6 , orthophosphoric acid is distributed uniformly in the active area of the MEA—its average content is 9.3 mg/cm2 with deviations of no more than 0.1 mg/cm2. There are no over-doped locations on the perimeter of the MEA, and the amount of H3PO4 is far from critical levels. - With reference to
FIG. 1 , the roll of MEAs is cut by aknife 13 to form sheets withsingle MEAs 14, which are moved on theconveyor belt 15 to the assembly table 16. The assembly table 16 has an adjustable height. Endplates for fuel cell stack are provided from magazine 17 and bipolar plate with gaskets from magazine 18. Further,bolts 19 are delivered by means of corresponding conveyors. - The build-up of the fuel cell stack occurs according to following step-by-step procedure with MEAs sandwiched between bipolar plates (BPP): For example, according to the following sequence:
- (I) endplate
- (II) bipolar plate (BPP)
- (III) MEA cut by
frame 14 - (IV) BPP
- and then repeating steps III and IV until a required amount of MEAs and BPP has been reached, after which another endplate is provided for finishing the stack.
-
Plate 20 creates correct compression to the stack, when the bolts and nuts are tightened. Assembled in such way, thefuel cell stack 21 is transported byfurther conveyor belt 15 to the carrier located on acargo robot 22 for its further storage. - As a conclusion, the proposed automated process of making MEAs and fuel cell stacks based on the MEAs has multiple advantages, such as continuity and fast speed by which high productivity and low costs are achieved. Uniform distribution of orthophosphoric acid in MEAs is properly controllable for avoiding critical levels. Two calendering stations are used, one for lamination and one for controlling acid levels at the edges and between the electrodes by local compression of predetermined parts of a MEA. This keeps the PBI membrane in a condition that is safe from dissolution by hot concentrated H3PO4 even without using protective gaskets on the perimeter of a MEA. The illustrated MEA is a 3-layer sandwich construction of a membrane between two electrodes, which is advantageous in comparison with the prior art 5-layer structure as described in reference [14].
- Moreover, when comparing polarization curves for MEAs with and without protective polyimide (PI) gaskets, it has been found that there is almost no difference between them when values are corrected for the actual active area. To investigate this, a comparative study was made. The results are presented and explained in the following with reference to
FIG. 7 andFIG. 8 , comparing membranes with and without PI gasket. - The actual electrode area is the same for both MEAs in
FIG. 7 , namely A×B cm2. However, whereas the 3-layer MEA without PI gaskets has a visible electrode area which is equal to the active area, namely A×B, this is not so for the 5-layer MEA with PI gaskets. In the latter case, first of all, it is observed that the 5-layer MEA with PI gaskets has a smaller visible electrode area, because 2 mm of the electrode on the perimeter is covered by a PI gasket. Although, about 1 mm of the electrode on each side under the PI gasket is not inert, it still results in an active area for the 5-layer MEA of (A−0.2)×(B−0.2) cm2. This implies that the prior art 5-layer MEA with the gaskets have a smaller active area if the overall dimensions of membrane and electrode otherwise are the same. - Observed was the following. Although, the 5-layer structure with the PI gaskets had a slightly higher performance per area, this was balanced in the 3-layer MEA by a slightly larger total active area. For greater detail, reference is made to
FIG. 8 a , which shows polarization curves for MEAs with and without PI gaskets where the measured current is normalized to the visible electrode area (a). It is observed that the MEA with PI gasket has a slightly higher performance experimentally. However, when the results are normalized to the actual active area, as explained in relation toFIG. 7 , no difference was found, as already mentioned above. Accordingly, the method of the invention is proven to provide equally good results as the prior art but with a much simpler procedure where gaskets are avoided. - In summary, the invention provides a continuous roll-to-roll process of MEA fabrication with already-doped membrane, in particular for high-temperature PEM fuel cells. The specific double calendering of the 3-layer MEA roll with only local compression along edge regions and between the electrodes protects the electrodes from disadvantageous pressure and avoids unwanted redistribution and overshooting of acid content. All in all, it leads to improved control of the dopant content and its distribution in the MEA.
-
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